TWI639468B - Stabilized rhenium-based heterogeneous catalyst and use thereof - Google Patents
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Abstract
本發明係關於一種穩定之錸系異相催化劑，其係由一製程所獲得，該製程包含將一錸系異相催化劑與一穩定劑於0至100℃之溫度下接觸，該穩定劑包含一脂族烴化合物；以及其應用。 The present invention relates to a stable lanthanide heterogeneous catalyst obtained by a process comprising contacting a lanthanide heterogeneous catalyst with a stabilizer at a temperature of from 0 to 100 ° C, the stabilizer comprising an aliphatic group Hydrocarbon compounds; and their use.
Description
本發明係關於一種穩定之錸系異相催化劑，及一種使用該催化劑製造一烯烴化合物之製程。 This invention relates to a stable ruthenium heterogeneous catalyst and a process for the manufacture of an olefinic compound using the catalyst.
複分解反應(metathesis reaction)係用於烯烴的轉化。在複分解反應中，相同或不同種類的烯烴與彼此反應以得到具有不同結構的烯烴，舉例而言，乙烯與丁烯複分解得到丙烯，以及丁烯複分解得到戊烯與丙烯。 The metathesis reaction is used for the conversion of olefins. In the metathesis reaction, the same or different kinds of olefins are reacted with each other to obtain olefins having different structures. For example, ethylene and butene are metathesized to obtain propylene, and butene is metathesized to obtain pentene and propylene.
已發展多種用於烯烴複分解的催化劑。在其中，具有承載於一高表面積載體的鉬、鎢、及錸的氧化物的催化劑得到產業的最高興趣。 A variety of catalysts have been developed for the metathesis of olefins. Among them, catalysts having oxides of molybdenum, tungsten, and rhenium supported on a high surface area carrier have received the industry's highest interest.
鉬系與鎢系催化劑較廣泛用於產業複分解製程，其係因為它們具有對於催化劑毒化物質的較高耐性，以及較低的成本。然而，已知它們相較於錸具有較低活性，而因此需要典型高於100℃且較佳高於200℃的較高溫度以達成理想活性。便利使用的較高溫度由於會發生副反應，例如烯烴異構化反應及寡聚反應，導致降低的選擇性。 Molybdenum and tungsten catalysts are widely used in industrial metathesis processes because of their high resistance to catalyst poisoning materials and low cost. However, they are known to have lower activity than ruthenium, and thus higher temperatures typically above 100 ° C and preferably above 200 ° C are required to achieve the desired activity. Higher temperatures that are convenient to use result in reduced side reactions due to side reactions such as olefin isomerization and oligomerization.
錸在烯烴複分解中具高活性。其可在顯著較低的溫 度範圍下操作。然而，其快速的去活化作用為主要不利點。 Rhodium is highly active in olefin metathesis. It can be at significantly lower temperatures Operate in the range of degrees. However, its rapid deactivation is a major disadvantage.
歐洲專利申請案EP 0273817 A1揭露一種烯烴複分解製程，其在移動床反應區中於錸催化劑存在下進行，其中催化劑之後在一連接的再生區中再氧化。此使得即使錸催化劑具有高去活化率，製程也可連續操作。然而，移動床製程尤其是相較於固定床系統係更加地複雜且耗能，因此在產業應用上通常較不理想。 European Patent Application EP 0273817 A1 discloses an olefin metathesis process which is carried out in the moving bed reaction zone in the presence of a rhodium catalyst, wherein the catalyst is then reoxidized in a connected regeneration zone. This allows the process to be operated continuously even if the rhodium catalyst has a high deactivation rate. However, moving bed processes are generally more complex and energy intensive than fixed bed systems and are therefore generally less desirable in industrial applications.
美國專利案US 6,277,781 B1揭露一種用於降低一錸系複分解催化劑的去活化率的方法，該方法包含：於進行複分解反應前，將該催化劑在高於750℃的溫度下於一含烴的流內，例如甲烷流，且在氫存在下進行處理，並在一非還原性氣氛內於400至1000℃的溫度下進行活化，且該催化劑較佳含有一份量的銫。 US Patent No. 6,277,781 B1 discloses a method for reducing the deactivation rate of a lanthanide metathesis catalyst, the method comprising: subjecting the catalyst to a hydrocarbon-containing stream at a temperature above 750 ° C prior to performing the metathesis reaction. Internally, for example, a methane stream is treated in the presence of hydrogen and activated at a temperature of 400 to 1000 ° C in a non-reducing atmosphere, and the catalyst preferably contains a one-component amount of ruthenium.
因此，本發明的一目標在於提供一種穩定之錸系異相催化劑以克服先前技術的不利點，尤其在於顯示出改進的反應穩定性與對於毒化物質的耐性。 Accordingly, it is an object of the present invention to provide a stable lanthanide heterogeneous catalyst to overcome the disadvantages of the prior art, particularly to exhibit improved reaction stability and resistance to poisoning materials.
本發明的另一目標在於提供一種穩定之錸系異相催化劑，其允許於一固定床反應器內使用該催化劑。 Another object of the present invention is to provide a stable lanthanide heterogeneous catalyst which permits the use of the catalyst in a fixed bed reactor.
本發明的又另一目標在於提供一種改進的用於製造烯烴化合物的製程，其中提高操作週期時間。 Still another object of the present invention is to provide an improved process for the manufacture of olefinic compounds wherein the cycle time is increased.
前述目標係藉由一種穩定之錸系異相催化劑及其製備製程而達成，其中該製程包含將一錸系異相催化劑與一穩定劑於低溫下接觸。 The foregoing objects are achieved by a stable ruthenium heterogeneous catalyst and a process for its preparation, wherein the process comprises contacting a lanthanide heterogeneous catalyst with a stabilizer at low temperatures.
更詳細而言，該目標係藉由一種穩定之錸系異相催 化劑而達成，該穩定之錸系異相催化劑係由一製程所獲得，該製程包含將一錸系異相催化劑與一穩定劑於0至100℃之溫度下接觸，該穩定劑包含一脂族烴化合物。 In more detail, the goal is based on a stable relationship The stable ruthenium heterogeneous catalyst is obtained by a process comprising contacting a lanthanide heterogeneous catalyst with a stabilizer at a temperature of from 0 to 100 ° C, the stabilizer comprising an aliphatic hydrocarbon Compound.
第1圖示出穩定劑於2-丁烯轉化率的效果。 Figure 1 shows the effect of the stabilizer on the conversion of 2-butene.
第2圖示出穩定劑於丙烯選擇性的效果。 Figure 2 shows the effect of the stabilizer on propylene selectivity.
第3圖示出穩定溫度於2-丁烯轉化率的效果。 Figure 3 shows the effect of stabilizing temperature on 2-butene conversion.
第4圖示出穩定溫度於丙烯選擇性的效果。 Figure 4 shows the effect of stabilizing temperature on propylene selectivity.
根據本發明的錸系異相催化劑含有金屬元素形式的錸及/或至少一種錸化合物(如氧化錸、氫化錸、硫化錸、碳化錸、或其任意組合)，其沉積於一固體載體上。 The lanthanide heterogeneous catalyst according to the present invention contains ruthenium in the form of a metal element and/or at least one ruthenium compound (e.g., ruthenium oxide, ruthenium hydride, ruthenium sulfide, ruthenium carbide, or any combination thereof) deposited on a solid support.
沉積有該錸化合物的固體載體可選自多種多孔材料。在一實施態樣中，該固體載體係選自由以下所組成之群組：Al2O3、Ga2O3、SiO2、GeO2、TiO2、ZrO2、SnO2、鋁矽酸鹽、活性碳、水滑石(hydrotalcite)、陰離子性黏土(anionic clay)、或其混合物；較佳係Al2O3、SiO2、或其混合物。適合的固體載體典型具有10至500平方公尺/公克之比表面積，較佳100至400平方公尺/公克。 The solid support on which the ruthenium compound is deposited may be selected from a variety of porous materials. In one embodiment, the solid support is selected from the group consisting of Al 2 O 3 , Ga 2 O 3 , SiO 2 , GeO 2 , TiO 2 , ZrO 2 , SnO 2 , aluminosilicate, Activated carbon, hydrotalcite, anionic clay, or a mixture thereof; preferably Al 2 O 3 , SiO 2 , or a mixture thereof. Suitable solid supports typically have a specific surface area of from 10 to 500 square meters per gram, preferably from 100 to 400 square meters per gram.
該錸系異相催化劑可藉由本領域已知製備異相催化劑的方法所製備。在一般情況下，錸系異相催化劑的製備係藉由如下方式進行：a)以一錸化合物溶液浸漬一固體載體，以及b)將該浸漬的載體進行後續乾燥及煅燒。 The lanthanide heterogeneous catalyst can be prepared by methods known in the art for preparing heterogeneous catalysts. In general, the preparation of the lanthanide heterogeneous catalyst is carried out by a) impregnating a solid support with a ruthenium compound solution, and b) subjecting the impregnated support to subsequent drying and calcination.
在催化劑中存在的錸分量通常基於催化劑的總重係 0.01%至20%。本發明的錸系異相催化劑可經進一步修改，包含適當的額外組分，以通常調整催化劑的性質。舉例而言，該催化劑可進一步含有例如鈀或鉑的過渡金屬之化合物以提供用於氫化反應之活性，或含有鹼金屬或鹼土金屬之化合物以提供用於異構化反應之活性。 The enthalpy component present in the catalyst is usually based on the total weight of the catalyst 0.01% to 20%. The lanthanide heterogeneous catalysts of the present invention can be further modified to include suitable additional components to generally tailor the properties of the catalyst. For example, the catalyst may further contain a compound of a transition metal such as palladium or platinum to provide activity for the hydrogenation reaction, or a compound containing an alkali metal or an alkaline earth metal to provide activity for the isomerization reaction.
錸系異相催化劑係與一穩定劑接觸以提供穩定之錸系異相催化劑。在一實施態樣中，該穩定劑包含一脂族烴化合物，較佳一含有2至6個碳原子之脂族烴化合物，更佳含有2至4個碳原子之烷或烯化合物。對本發明而言，包含n個碳原子的化合物標示為Cn化合物。意即，舉例而言，一C2脂族烴化合物可為乙烷、乙烯、或乙炔。在較佳實施態樣中，該穩定劑係選自由以下所組成的群組：乙烷、乙烯、丙烷、丙烯、丁烷、丁烯或其混合物。 The lanthanide heterogeneous catalyst system is contacted with a stabilizer to provide a stable lanthanide heterogeneous catalyst. In one embodiment, the stabilizer comprises an aliphatic hydrocarbon compound, preferably an aliphatic hydrocarbon compound having 2 to 6 carbon atoms, more preferably an alkane or olefin compound having 2 to 4 carbon atoms. For the purposes of the present invention, compounds containing n carbon atoms are designated as Cn compounds. That is, for example, a C2 aliphatic hydrocarbon compound can be ethane, ethylene, or acetylene. In a preferred embodiment, the stabilizer is selected from the group consisting of ethane, ethylene, propane, propylene, butane, butylene or mixtures thereof.
進行將穩定劑與錸系異相催化劑接觸的條件必須謹慎選擇以使得催化劑穩定。較佳地，係於0至100℃之溫度下接觸，較佳10至60℃，更佳20至40℃。在一較佳實施態樣中，該接觸條件包括1至50巴(bar)之壓力，較佳10至30巴。較高的溫度及/或更劇烈的接觸條件傾向於導致在錸活性位置上生成碳質物質，結果使催化劑去活化。 The conditions for contacting the stabilizer with the lanthanide heterogeneous catalyst must be carefully selected to stabilize the catalyst. Preferably, it is contacted at a temperature of from 0 to 100 ° C, preferably from 10 to 60 ° C, more preferably from 20 to 40 ° C. In a preferred embodiment, the contact conditions comprise a pressure of from 1 to 50 bar, preferably from 10 to 30 bar. Higher temperatures and/or more severe contact conditions tend to result in the formation of carbonaceous materials at the active sites of the hydrazine, with the result that the catalyst is deactivated.
該穩定之錸系異相催化劑在以穩定劑處理後，由於吸附的穩定劑，錸活性位置的疏水性質顯現改變。此使得催化劑對烯烴原料更具選擇性，且對催化劑毒化物質活性較低，尤其是致氧化物質(oxygenate substance)。 The stable ruthenium heterogeneous catalyst exhibits a change in the hydrophobic nature of the active site of the ruthenium after treatment with the stabilizer due to the adsorbed stabilizer. This makes the catalyst more selective for olefinic feedstocks and less active towards catalyst poisoning materials, especially oxygenate substances.
根據本發明的製程為簡單的，並不需要劇烈的操作 條件，且令人驚訝地得到一穩定之錸系異相催化劑，其具有改進的反應穩定性以及對於毒化物質的耐性。 The process according to the invention is simple and does not require violent operation Conditions, and surprisingly, a stable lanthanide heterogeneous catalyst with improved reaction stability and resistance to poisoning materials is obtained.
該穩定之錸系異相催化劑可於數種反應製程中有益地使用，其中錸可提供適當的反應活性，舉例而言，烯烴環氧化反應、醇氧化反應、及尤其是複分解反應。 The stable ruthenium heterogeneous catalyst can be advantageously used in several reaction processes wherein ruthenium provides suitable reactivity, for example, olefin epoxidation, alcohol oxidation, and especially metathesis.
本發明亦關於使用前述穩定製程獲得的穩定之錸系異相催化劑製造烯烴化合物的製程。該製程包含將該穩定之錸系異相催化劑與一烯烴進料流接觸。 The present invention also relates to a process for producing an olefinic compound using a stable lanthanide heterogeneous catalyst obtained by the foregoing stable process. The process comprises contacting the stabilized lanthanide heterogeneous catalyst with a monoolefin feed stream.
本發明之目標更由一種製備烯烴化合物之製程所達成，該製程包含將根據本發明之穩定之錸系異相催化劑與一烯烴進料流接觸，其中該烯烴進料流包含至少一烯烴，其選自C2至C12烯烴或其混合物，且該接觸係於0至300℃之溫度下進行，較佳10至100℃，更佳20至60℃。 The object of the present invention is further achieved by a process for the preparation of an olefinic compound comprising contacting a stabilized lanthanide heterogeneous catalyst according to the present invention with an olefin feed stream, wherein the olefin feed stream comprises at least one olefin, selected From C2 to C12 olefins or mixtures thereof, and the contacting is carried out at a temperature of from 0 to 300 ° C, preferably from 10 to 100 ° C, more preferably from 20 to 60 ° C.
將該烯烴進料流與該穩定之錸系異相催化劑接觸係於使該進料流轉換為理想烯烴產物的允許條件(enabling condition)下進行。較佳地，該允許條件包括0℃至100℃之溫度，更佳10℃至80℃，最佳20℃至60℃之溫度。 Contacting the olefin feed stream with the stabilized lanthanide heterogeneous catalyst is carried out under an enabling condition to convert the feed stream to the desired olefin product. Preferably, the allowable conditions include a temperature of from 0 ° C to 100 ° C, more preferably from 10 ° C to 80 ° C, and most preferably from 20 ° C to 60 ° C.
可在根據本發明的穩定之錸系異相催化劑存在下被轉化為一烯烴化合物的烯烴進料流可為至少一種具有2至12個碳原子的烯烴，較佳2至6個碳原子。該烯烴進料流可含有能進行自身反應(例如於自身複分解反應(auto-metathesis reaction))之單一物種的烯烴，以製造不同的烯烴。在更為一般之情況下，該烯烴進料流可含有多於一物種的烯烴，其可彼此反應以製造不同的烯烴。 The olefin feed stream which can be converted to the monoolefin compound in the presence of a stable lanthanide heterogeneous catalyst according to the present invention can be at least one olefin having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms. The olefin feed stream can contain a single species of olefin capable of undergoing a self reaction (e.g., in an auto-metathesis reaction) to produce different olefins. In a more general case, the olefin feed stream can contain more than one species of olefins that can react with each other to produce different olefins.
在本發明一特定實施態樣中，製造烯烴化合物的製程包含將根據本發明製程獲得的穩定之錸系異相催化劑與一烯烴進料流接觸，該烯烴進料流包含C2及C4直鏈烯烴之混合物及/或C2及C5直鏈烯烴之混合物。 In a particular embodiment of the invention, the process for making an olefinic compound comprises contacting a stabilized lanthanide heterogeneous catalyst obtained in accordance with the process of the present invention with an olefin feed stream comprising C2 and C4 linear olefins. Mixtures and/or mixtures of C2 and C5 linear olefins.
在該烯烴進料流包含C4直鏈烯烴的實施態樣中，該C4直鏈烯烴可以C4直鏈烯烴、非直鏈烯烴、二烯烴、及鏈烷烴(paraffin)的混合物的形式提供。該混合物通常被稱作「C4餾分(C4-cut)」，其係通常由製造烯烴的熱裂解製程所製造的流。在進入根據本發明之製程前，將C4餾分經過預處理製程通常是有益的。該預處理製程可包括轉換及某些組分的分離，並且僅留下能在接觸根據本發明的穩定之錸系異相催化劑時反應轉換為理想烯烴產物的組分。C4餾分預處理製程的實例可見於美國專利US 5,877,365、US 5,898,091、及US 6,075,173中。 In embodiments where the olefin feed stream comprises a C4 linear olefin, the C4 linear olefin can be provided as a mixture of C4 linear olefins, non-linear olefins, diolefins, and paraffins. This mixture is commonly referred to as "C4-cut", which is a stream typically produced by a thermal cracking process for the manufacture of olefins. It is generally beneficial to subject the C4 cut to a pretreatment process prior to entering the process according to the present invention. The pretreatment process can include conversion and separation of certain components, and leaving only components that can be converted to the desired olefin product upon contact with a stable lanthanide heterogeneous catalyst according to the present invention. Examples of the C4 fraction pretreatment process can be found in U.S. Patent Nos. 5,877,365, 5,898,091, and 6,075,173.
更詳細而言，本發明係關於一種用於製造烯烴化合物之製程，包含將根據本發明之穩定之錸系異相催化劑與一烯烴進料流接觸，該烯烴進料流包含一選自C2至C12之烯烴(較佳C2至C6直鏈烯烴)及其混合物，該接觸係於烯烴進料流可轉化為理想烯烴產物的允許溫度下進行，較佳0至300℃，更佳10至100℃，最佳20至60℃。 More particularly, the present invention relates to a process for the manufacture of an olefinic compound comprising contacting a stabilized lanthanide heterogeneous catalyst according to the present invention with an olefin feed stream comprising a selected from the group consisting of C2 to C12 An olefin (preferably a C2 to C6 linear olefin) and mixtures thereof, which are carried out at an allowable temperature at which the olefin feed stream can be converted to the desired olefin product, preferably from 0 to 300 ° C, more preferably from 10 to 100 ° C, Best 20 to 60 ° C.
再更詳細而言，本發明係關於一種用於製造丙烯的製程，該製程包含將根據本發明製程獲得的穩定之錸系異相催化劑在10至100℃溫度下與一包含C2及C4烯烴之混合物或C2及C5烯烴之混合物的烯烴進料流接觸。 In still more detail, the present invention relates to a process for the manufacture of propylene comprising a stabilized lanthanide heterogeneous catalyst obtained according to the process of the invention at a temperature of from 10 to 100 ° C and a mixture comprising C 2 and C 4 olefins Or the olefin feed stream of a mixture of C2 and C5 olefins is contacted.
在某些實施態樣中，該用於製造烯烴的製程係於1 至50巴的壓力及0.1至100h-1(小時-1)的每時之重量空間速度(WHSV，weight hourly space velocity)下進行。 In certain embodiments, the process for making olefins is at a pressure of from 1 to 50 bar and a weight hourly space velocity (WHSV) of from 0.1 to 100 h -1 (hour -1 ). get on.
在根據本發明的用於製造烯烴的製程中所使用的催化劑一般將逐漸隨時間去活化，因此需要週期地再生該催化劑。可以不受限制地使用任何已知用於異相催化劑再生的技術。該再生製程一般涉及脫附以及燒去任何吸附的碳質物種，並同時於稀釋空氣流動下在300至800℃溫度再煅燒。該再生使得至少部分的，或甚至在某些情況下全部的，使催化劑的催化效能恢復。在某些實施態樣中，根據本發明的製備穩定之錸系異相催化劑的製程可便利地直接在催化劑再生製程之後及下一個反應週期之前進行。 The catalyst used in the process for producing olefins according to the present invention will generally be gradually deactivated over time, thus requiring periodic regeneration of the catalyst. Any technique known for heterogeneous catalyst regeneration can be used without limitation. The regeneration process generally involves desorption and burning off any adsorbed carbonaceous species and simultaneously calcining at a temperature of 300 to 800 °C under dilution air flow. This regeneration allows at least some, or even in some cases all, recovery of the catalytic performance of the catalyst. In certain embodiments, the process for preparing a stable lanthanide heterogeneous catalyst in accordance with the present invention can be conveniently carried out directly after the catalyst regeneration process and prior to the next reaction cycle.
較佳地，根據本發明的製造烯烴的製程係於一固定床反應器內進行。 Preferably, the process for producing olefins according to the present invention is carried out in a fixed bed reactor.
最後，本發明的目標係藉由將根據本發明的穩定之錸系異相催化劑用於催化碳氫轉化反應所達成。 Finally, the object of the invention is achieved by the use of a stable lanthanide heterogeneous catalyst according to the invention for catalyzing a hydrocarbon conversion reaction.
由根據本發明製程所製備的穩定催化劑使得製造烯烴化合物的製程，其較佳藉由複分解反應，得以於各次再生之間以更長的操作週期進行操作。舉例而言，在本發明用於由包含C4餾分與乙烯的混合物之進料流製造丙烯的製程之一具體實施中，該穩定之錸系異相催化劑顯示出大約3倍長的操作週期，相較於由習知製備方法製備而未經過根據本發明穩定的錸系異相催化劑。在某些實施態樣中，根據本發明將錸系異相催化劑與穩定劑接觸係藉由將該錸系異相催化劑提供於一固定床反應器中，並將一包含該穩定劑的液體流流經該提供的催化劑床，之後接著將該 穩定之催化劑與一烯烴進料流於反應條件下接觸而進行。 The stable catalyst prepared by the process according to the present invention allows the process for producing an olefin compound, which is preferably operated by a metathesis reaction with a longer cycle of operation between regenerations. For example, in one embodiment of the process for making propylene from a feed stream comprising a mixture of a C4 cut and ethylene, the stabilized lanthanide heterogeneous catalyst exhibits an approximately three times longer cycle of operation than The ruthenium heterogeneous catalyst prepared by the conventional preparation method without being stabilized according to the present invention. In certain embodiments, the lanthanide heterogeneous catalyst is contacted with a stabilizer in accordance with the present invention by providing the lanthanide heterogeneous catalyst in a fixed bed reactor and flowing a liquid stream comprising the stabilizer The provided catalyst bed, which is then The stable catalyst is contacted with a monoolefin feed stream under reaction conditions.
下列實施例示出本發明實施態樣，但並不限制其範圍。 The following examples illustrate the embodiments of the invention, but do not limit the scope thereof.
實施例Example
根據發明製備了數種催化劑，並與根據先前技術製備的催化劑比較。催化劑的組成如下：催化劑A(比較)係一未經穩定之γ-氧化鋁載體上之氧化錸催化劑。 Several catalysts were prepared according to the invention and compared to catalysts prepared according to the prior art. The composition of the catalyst was as follows: Catalyst A (comparative) was a ruthenium oxide catalyst on an unstabilized γ-alumina support.
根據本發明之催化劑B、C、D及E係γ-氧化鋁載體上之氧化錸催化劑，其係藉由穩定氣體於穩定溫度下流經該催化劑之固定床而穩定的。 The catalysts of Groups B, C, D and E on the gamma-alumina support according to the present invention are stabilized by a stable gas flowing through a fixed bed of the catalyst at a stable temperature.
催化劑F、G、及H(比較)係γ-氧化鋁載體上之氧化錸催化劑，其藉由穩定氣體於高溫下流經該催化劑之固定床而預處理的。 Catalysts F, G, and H (comparative) are ruthenium oxide catalysts on a gamma-alumina support which are pretreated by stabilizing the gas flowing through a fixed bed of the catalyst at elevated temperatures.
催化劑A至H係用於複分解反應測試中。測試係藉由將12公克/小時之C4烯烴混合物與120sccm(標準立方公分/分鐘)乙烯於30℃溫度及20巴壓力下，流經6公克催化劑試樣之固定床而進行。細節與測試結果係顯示於表1中。 Catalysts A to H were used in the metathesis reaction test. The test was carried out by flowing a 12 g/h C4 olefin mixture with 120 sccm (standard cubic centimeters per minute) of ethylene at a temperature of 30 ° C and a pressure of 20 bar through a fixed bed of 6 g of the catalyst sample. Details and test results are shown in Table 1.
由測試編號1及2可觀察到進料流中的致氧化物質顯然影響催化劑的去活化。在測試編號3、4、5、及6中，結果顯示使用根據本發明的穩定之錸系異相催化劑顯著降低了致氧化物質的效應。 It was observed from Test Nos. 1 and 2 that the oxidizing species in the feed stream apparently affected the deactivation of the catalyst. In Test Nos. 3, 4, 5, and 6, the results show that the use of the stabilized lanthanide heterophasic catalyst according to the present invention significantly reduces the effect of the oxidizing species.
並且，在測試編號3、4、5、及6中，可見多種烴化合物可作為本發明之穩定劑。 Further, in Test Nos. 3, 4, 5, and 6, it is seen that various hydrocarbon compounds can be used as the stabilizer of the present invention.
在測試編號7、8、及9中，可見從發明角度，較高溫度並不會得到穩定的催化劑。相反地，其對於催化劑效能造成顯著不利效應。 In Test Nos. 7, 8, and 9, it can be seen from the perspective of the invention that a higher temperature does not result in a stable catalyst. Conversely, it has a significant adverse effect on catalyst performance.
在乙烯與混合C4流以製造丙烯的複分解反應中，使用藉由不同穩定劑穩定的催化劑及未經穩定的催化劑(標示為「習知預處理」)的比較結果係示於第1圖及第2圖中。 In the metathesis reaction of ethylene and mixed C4 stream to produce propylene, the comparison between the catalyst stabilized by different stabilizers and the unstabilized catalyst (labeled as "pre-treatment") is shown in Figure 1 and 2 in the picture.
在乙烯與混合C4流以製造丙烯的複分解反應中，使用藉由不同穩定溫度穩定的催化劑及未經穩定的催化劑(標示為「習知預處理」)的比較結果係示於第3圖及第4圖中。 In the metathesis reaction of ethylene and mixed C4 streams to produce propylene, the comparison results using catalysts stabilized by different stable temperatures and unstabilized catalysts (labeled as "pre-treatment") are shown in Figure 3 and 4 in the picture.
以上敘述所揭露的特徵，於申請專利範圍及/或於後附圖式中，皆可分別或以任何組合作為以多種形式實現本發明的材料。 The features disclosed in the above description, in the scope of the patent application and/or in the following figures, may be implemented in various forms, respectively, or in any combination.
實行發明之最佳態樣Implement the best aspect of the invention
實踐本發明之最佳態樣係描述於前述【實施方式】部分。 The best mode for carrying out the invention is described in the aforementioned [Embodiment] section.
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| FR2608595B1 (en) | 1986-12-17 | 1989-04-28 | Inst Francais Du Petrole | PROCESS FOR THE METATHESIS OF OLEFINS |
| FR2733986B1 (en) | 1995-05-11 | 1997-06-13 | Inst Francais Du Petrole | PROCESS AND INSTALLATION FOR THE CONVERSION OF OLEFINIC C4 CUTS INTO POLYISOBUTENES AND PROPYLENE |
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